Improved Local-Mode Zero-Point-Energy Conservation Scheme for Quasiclassical Trajectories

Abstract

We present an improvement of the local-pair zero-point-energy (LP-ZPE) scheme of Mukherjee and Barbatti. The new approximation is called the improved LP-ZPE scheme or iLP-ZPE. This scheme can produce trajectories that do not have unphysical leaking of zero-point energy from high-frequency spectator modes into low-frequency modes. We illustrate the method with a successful direct dynamics application to the Ne•••HF van der Waals molecule. The method is well suited for direct dynamics calculations because it does not require costly evaluations of local Hessians or instantaneous normal modes along the trajectories.